Accelerating the reaction kinetics of K₂CO₃ through the addition of CsF in the view of thermochemical heat storage

Potassium carbonate (K2CO3) is a promising thermochemical heat storage material (TCM). However, it suffers from hysteresis between (de)hydration temperatures and poor reaction kinetics close to equilibrium conditions. Both aspects are caused by a nucleation barrier and low ionic mobility close to equilibrium. This study investigates the impact of caesium fluoride (CsF) incorporated through recrystallisation on the phase transitions. The composition studies show that K2CO3and CsF react during synthesis, forming KF, which points to the formation of Cs2CO3. The secondary phases are not incorporated into the crystal structure but reside between the main phase's grain cracks due to capillary forces. Because the secondary phases are highly hygroscopic, they promote surface mobility by forming a liquid-like layer even at low water vapour pressures. As the effect of their presence, hydration kinetics are enhanced significantly in all investigated conditions, with the most pronounced impact when hydration of K2CO3is inherently inhibited. The benefits manifest themselves through a faster reaction rate and shorter induction period. The dehydration is enhanced by the presence of the additive mainly far away from equilibrium conditions. Close to the equilibrium, the dehydration of the composite proceeds in an unusual 2-step manner, where the second step is much slower than the dehydration of pure K2CO3. The enhancement of dehydration kinetics is ascribed to the formation of defects during recrystallisation. The lowering of dehydration rates close to equilibrium is attributed to diffusion issues due to excess of a deliquescent phase present in the system.